ITMI20130855A1 - METHOD OF COATING WITH POLYMER FILM OF A SUBSTRATE BY MEANS OF DEPOSITION AND SUBSEQUENT POLYMERIZATION BY PLASMA TREATMENT OF A MONOMERIC COMPOSITION. - Google Patents

Description

â € œMethod of coating a substrate with polymeric film by deposition and polymerization by aplasma treatment of a monomer composition.â €

FIELD OF INVENTION

The present invention relates to a method of coating a substrate with a polymeric film by depositing and polymerizing a monomer composition for plasma treatment.

STATE OF THE TECHNIQUE

At the state of the art, functional coatings on materials are made with industrial polymerization processes consisting of several processing steps of the material, including one of deposition by spreading / spraying of precursors containing polymerization initiators, and one of polymerization ( radical or ionic) operated by thermal energy, ultra violet (UV) or electronic radiation (EB).

In any case, chemical initiators are used which facilitate polymerization and increase the stability of the deposit. The use of polymerization initiators is necessary, for example, for radical polymerization by UV systems and for ionic polymerization by both UV and EB systems. The quantity of photoinitiator in the formulation, depending on the system being considered, can vary from 0.5 to 15%. In addition to being very expensive, photoinitiators are also very often toxic to human health, so systems capable of curing without their aid are highly desirable.

Furthermore, if the process is radicalic polymerization, the polymerization (thermal, UV or EB) must take place in the absence of oxygen.

In fact, oxygen represents a strong inhibitor for this type of polymerization, and currently the most used strategies to avoid this contamination are curing in an inert atmosphere (nitrogen atmosphere), the use of particular photoinitiators, the increase in intensity. of UV radiation, the use of oxygen scavengers and the use of waxes or shielding films. As for UV curing, the addition of waxes or other airtight compounds is known to reduce the inhibitory effect of oxygen. To improve surface curing in high-speed processes, the oxygen barrier concept was adopted to develop a technology consisting of a gelatin layer containing a high concentration of initiator which is applied over the formulation. This surface layer not only prevents the diffusion of oxygen from the surrounding environment, but is capable of providing an additional amount of initiator during UV irradiation. Furthermore, since the gelatin is not polymerizable under the action of UV radiation, the layer can therefore be easily removed by washing in water after crosslinking (curing). The results obtained using wax-based barriers are comparable with those obtained by working in a controlled atmosphere of inert gas (for example nitrogen).

Alternative methods for surface modification of materials being tested use plasmas produced in vacuum or at atmospheric pressure. In particular, plasmas can be used to obtain coatings of various thickness (of the order of less than one micron or one micron) with various functional properties. The material treatment process consists in mixing the precursor, gaseous or in the vapor phase, in a gas, typically noble or inert, creating a plasma with this mixture in order to fragment and dissociate the precursor molecules to obtain chemically reactive groups to be deposit on the substrate.

The deposition process occurs in most cases through a radicalic polymerization phase that requires an oxygen-free environment.

The vacuum processes have the advantage of being carried out in a controlled pressure environment and with inert gases with very low oxygen contamination, but they use expensive vacuum equipment and containment chambers in which it is possible to apply the treatments in a roll-to-configuration. roll.

At atmospheric pressure the problem of oxygen contamination can be overcome by inserting the plasma source in a suitable containment chamber that simulates a closed and controlled environment, in which through openings allow the continuous treatment of materials in an oxygen-free environment. Atmospheric plasma is necessarily produced in a mixture of an inert or noble gas, typically nitrogen, which acts as a carrier gas for the precursor to be polymerized. WO 02/28548 describes a method for the deposition of functional coatings by combining a plasma discharge at atmospheric pressure and an atomized precursor. In this way it is possible to deposit a series of coatings which largely maintain the functionality of the monomer used.

WO 2003/085693 discloses an atmospheric pressure plasma process, in which a process gas and an atomized precursor are introduced into the plasma region between the electrodes.

US 8178168 describes a method in which for the deposition of polymer coatings, a mixture containing a radical polymerizable monomer and a radical initiator are plasma treated at atmospheric pressure and the resulting polymer coating is deposited on a substrate. The plasma is preferably generated with inert gases (argon, helium) or with mixtures of the same with other gases (air, nitrogen, oxygen, ammonia, water vapor). The substrate can be previously activated by means of another plasma treatment at atmospheric pressure.

The possibility of depositing functional coatings on different substrates through multi-step processes (low pressure plasma pre-activation - impregnation with a monomer - low pressure plasma treatment) is well documented in the literature. See, for example, the following scientific publications: M.J. Tszfack et al., Surface & Coating Technology 200 (2006) 3503-3510. In all cases the plasma treatments, in addition to being carried out in closed rooms at low pressure, are carried out with the use of inert gases and therefore in conditions of very low oxygen contamination.

Similar procedures are also carried out through the use of plasma treatments at atmospheric pressure (see, for example, C. Chaiwong et al., Surface & Coating Technology 204 (2010) 2991-2995). Even in this, however, it is necessary that the gas with which the plasma is produced is inert or noble to avoid the presence of oxygen which would inhibit the radical polymerization process.

WO 2003/089479 describes a method for coating a substrate by depositing a monomer composition containing a mixture of ionically and / or radical polymerizable monomers and subsequent plasma treatment. In this type of process, however, the presence of a radical photocatalyst is essential, if the polymerization takes place with a radical mechanism and, if the polymerization takes place by ionic pathway, an ionic catalyst, i.e. components that, as highlighted above, pollute the coating and consequently the final coated material. Furthermore, even in this type of process the plasma treatment is carried out under vacuum or in the presence of inert gases.

The need is therefore felt to have a process for coating a substrate with a polymeric film substantially free from photocatalysts.

The need is also felt to have a process for coating a substrate with a substantially simple polymeric film, easily scalable and applicable in industrial continuous coating processes.

SUMMARY OF THE INVENTION

The Applicant has surprisingly found a process which does not present the problems of the state of the art.

The object of the present invention is in fact a method of coating a substrate comprising the following stages:

a) deposition on said substrate of a polymerizable composition selected from the following compositions:

composition (A) containing as essential component: at least one epoxy monomer (i) and / or a silicone epoxy monomer (ii);

composition (B) containing as an essential component at least one silicone epoxy monomer (ii) and at least one monomer containing at least one ethylene unsaturation (iii);

b) polymerization of said composition by plasma treatment.

The coating obtained with this method is substantially free of ionic photocatalysts.

The Applicant has also surprisingly found that the method object of the present invention can be carried out in plasma in the presence of air.

DESCRIPTION OF THE FIGURES

Figure 1 represents the absorption time of 50 microliter drops of water on the material coated with the composition of Example 9 untreated and heated as a function of the heating time and of the material coated with the method according to the present invention for plasma treatment.

Figure 2 represents a photograph enlarged at 1498X (1498 enlargements) under the scanning electron microscope of the substrate (cotton 2) before being coated with the method according to the present invention and described in example 16.

Figure 3 represents an enlarged photograph at 2620X of the substrate (cotton 2) coated with the method of the present invention and prepared as described in example 16 obtained by polymerization of an epoxy silicone (ii)

Figure 4 represents an enlarged photograph at 2519X of the substrate (cotton 2) according to the method of the present invention and prepared as described in example 16 obtained by polymerization of an epoxy silicone incorporating nano particles of titanium dioxide.

DETAILED DESCRIPTION OF THE INVENTION

For the purposes of the present invention, by polymerization we mean the polymerization of a monomer, such as that of the monomer of type (i) or that of the monomer of type (iii), or the crosslinking of a polymer / oligomer such as that which takes place using the monomer of type (ii). The definition of monomer for the purposes of the present invention means both a real monomer and an oligomer / polymer of the type capable of further polymerizing.

For the purposes of the present invention with the definition â € œthe composition (A) / (B) contains as an essential componentâ € it is meant to underline that the composition used in the method object of the present invention, in addition to the monomers of type (i) and (ii ) for the composition (A) and the monomers of type (ii) and (iii) of the composition (B) does not require further components essential for the relative polymerization, unlike what occurs in the method described in WO 2003/089479, where At least the presence of polymerization photocatalysts is essential.

A comparison of the aforementioned definition is however broadly confirmed in the comparative tests reported in the present description, where it is highlighted that the method of the invention conducted in the absence of photocatalysts allows to obtain coatings with comparable characteristics and in some cases better than those obtained in the presence of photocatalysts.

Therefore, the object of the present invention is a coated substrate obtained by deposition and subsequent plasma polymerization on said substrate of a composition of type (A) or (B) substantially free of radical polymerization initiators and ionic type photocatalysts.

For the purposes of the present invention, the definition of `` substantially free '' means that the aforementioned coating has a quantity of ionic photocatalyst lower than 5000 ppm (0.5%), preferably lower than 1000 ppm, more preferably lower than 500 ppm even more preferably at 100 ppm, by weight on the total weight of the coating of said substrate, preferably it is completely free of photocatalyst for ionic polymerization.

The composition (A) or (B) in step (a) of the method according to the present invention is preferably in liquid form, for example in the form of pure monomer or as such (or mixture of pure monomers in the absence of solvents), or in the form of a solution / suspension.

If the composition (A) or (B) is in the form of pure monomer or mixture of monomers, in the method according to the present invention, the monomer or mixture of monomers, possibly preheated, is applied to increase its spreadability / wettability on the substrate to be coated.

As highlighted above, the monomeric composition (A) or (B) can be applied in the form of a solution or a suspension in a solvent which can be organic or a mixture of water and one or more water-soluble organic solvents. The solvent must be volatile enough to allow its removal by evaporation at the end of the phase. Suitable solvents include for example ketones (methyl ethyl ketone, isobutyl methyl ketone etc.,) ethers (dioxane, tetrahydrofuran, 1,2 dimethoxyethane) esters (ethyl acetate, propyl acetate), alcohols (isopropanol), alkoxy alcohols (2-methoxyethanol) , 2-ethoxyethanol, 1-methoxy-2 propanol, or mixtures of these solvents with water.

Alternatively, water alone can also be used as a solvent, possibly combining the use of suitable surfactants.

Alcohols are preferably used, even more preferably isopropanol is used.

The deposition of the composition can be carried out with a series of techniques such as: spin coating, immersion, knife coating, brush application, spraying, electrostatic spraying, atomization, vaporization and reverse roller coating ( reverse roll coating), electrophoresis.

All techniques can include the use of rollers or rotors and wringing and / or drying processes. The deposition of the composition with all the techniques listed above can be carried out at a temperature different from the ambient temperature, for example at temperatures between 0 ° C and 150 ° C, keeping the composition itself and / or the deposition apparatus at the chosen temperature. .

The deposition of the composition can be carried out in several phases, for example by using the above-mentioned techniques and / or combinations of these in order to obtain different types of coatings, even with multiple layers.

It is also possible, by mixing different phases, to deposit micrometric, submicrometric and nanometric particles.

The composition is preferably deposited by means of a spray technique, by means of nebulizers, vaporizers, pneumatic atomizers or pressure atomizers or ultrasonic or vibrating atomizers.

Alternatively, it is also possible to use fluid bed technologies for the deposition of fluids containing particles of various compositions (dyes, conductors,

semiconductors, â € ¦).

Surprisingly, it has also been found that the polymerization or step (b) of the method object of the present invention can be carried out in the presence of air, therefore in plants which do not provide for the presence of equipment and lines for vacuum and / or inert materials.

Stage (b) can be carried out using various types of plasma sources, such as dielectric barrier discharge - DBD, surface dielectric barrier discharge (SDBD), Corona, glow discharge. , plasma beam (Plasma Jet), remote plasmas (for which the plasma is generated in a given area from which it is then extracted thanks to directed gas flows and / or by pressure difference and or magnetic fields and or electromagnetic drifts, (Micro -Hollow) for which a series of packaged hollow tubes that acting either as an RF radio frequency or as a ground are used to trigger a plasma), microwaves.

The aforementioned types of sources can be used both for limited areas and for large areas. The relative arrangement of the support coated with the monomer composition with respect to the plasma sources that allow its polymerization can be of different types, so that:

These types of sources have at least one electrode to generate the plasma (SDBD) or more electrodes (DBD) and the distance of the monomer composition from the electrode (s) is between 0 and 3 cm, or have more coplanar electrodes between which the plasma is produced and the monomer composition, preferably parallel to them, is placed at a distance between 0 and 3 cm. One or each electrode may be coated with dielectric material. One or more electrodes can be grounded or can be floating. At least one is powered with voltage and frequency currents between direct current (DC) and Microwave. For the configuration in direct contact between the material and the electrodes, a resistivity of the material higher than the resistivity of the gas in the plasma state is required;

The support with the monomer composition is in a configuration suitable for receiving a plasma beam extracted from a region in which it is generated (plasma jet or plasma beam). In this case the material is located at a distance from the aforesaid region comprised between a few mm and 15 cm, preferably between 0.5 and 10 cm.

Preferably DBD is used as a plasma source. The plasma treatment temperatures of the coating method according to the present invention are those typical of cold plasmas. The operating frequencies of the aforementioned types of plasma generators and, as reported above, can vary from those typical of direct current (DC) up to Microwaves, therefore they can reach values up to 10 <6> MHz. More preferably between 300 Hz and 10 <5> MHz, even better between 10 <3> Hz and 10 <4> MHz. For DBD generators the optimal frequencies are from 0.5kHz to 1MHz. The direct current (DC) source can work in direct current or pulsed current. In any case, according to the method of the invention, generators at cyclotronic resonance frequencies can also be used to ignite the plasma. The operating pressures vary from 0.5 atm up to 3 atm. In particular, the ideal working conditions are between 90% and 150% of the ambient pressure. Finally, the operating powers are generally between 1 W / cm and 500 W / cm, preferably between 10 W / cm and 300W / cm.

If the Plasma Jet type source is used, including plasma needle and plasma blaster, the operating powers are between 10W / cm and 2000 W / cm, the working frequencies are between DC and Radio Frequency.

The operating temperature of stage (b) is preferably lower than 150 ° C, even more preferably stage (b) is carried out at room temperature.

In a preferred embodiment, the method of coating a substrate object of the present invention can provide before step (a) a plasma pretreatment of the substrate to be coated in order to increase the wettability of the substrate and / or the uniformity of the coating. and / or the adhesion of the coating to the surface of the substrate on which the coating is applied.

With the method object of the present invention it is possible to impart to the substrate to be coated different surface characteristics deriving from the specific monomer or mixtures of monomers used. These characteristics (such as for example water repellency, hydrophilicity, oil repellence, â € ¦) can be imparted individually or in combination (multifunctionality), such as for example water repellency associated with oil repellency.

Type (i) epoxy monomers are preferably selected from: glycidol, styrene oxide, butadiene oxide, ethylene glycol diglycidyl ether, glycidyl methacrylate, bisphenol A diglycidyl ether (and its oligomers), 1,2 epoxydecane, glycerol diglycidyl ether, 1,4 butanediol-diglycidyl ether, 1,3 diglycidylglyceryl ether, glycidyl octafluoropentyl ether, propylene oxide, glycidyl methyl ether, glycidyl butyrate, cyclohexene oxide, epoxyoctane, glycidyl tosylate, diepoxyoctane, furfuryl glycidyl ether, (2,2,3,3, 4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl) oxirane. The epoxy monomers of type (i) indicated above containing in addition to the epoxy group also a hydroxyl group are able to impart hydrophilicity, on the contrary those without the aforementioned hydrophilic groups are able to substantially impart water repellency The silicone epoxy monomer of type (ii ), Is able to impart water repellency. The monomer of type (ii) can be selected from a low molecular weight and preferably low viscosity epoxy silicone monomer, such as for example 2- (3,4-epoxycyclohexyl) ethyltriethoxy silane or 2- (3,4-epoxycyclohexyl) - ethyltrimethoxy silane or a C1-C4-alkyl siloxane oligomer / polymer, being terminated with and / or being substituted in the chain with at least one C1-C6alkylene (C5-C6-cycloalkylene) -epoxide residue, even more preferably this type of monomer à ̈ characterized by the following formulas (I) - (VII)

where m is an integer between 2 and 100, n is an integer between 2 and 10, R is a divalent C1-C6 alkylene residue, R <1> is a monovalent C1-C10 alkyl residue,

On the contrary, the Applicant has found, as already pointed out previously, that this class of epoxy monomers (ii) in analogy with the non-siliconized epoxy monomers of type (i), when used in the method according to the present invention, they do not need the aforesaid photocatalysts of ionic type.

The Applicant has also surprisingly found that with the method of the invention it is possible to polymerize the monomers containing at least one type (iii) ethylene unsaturation in the absence of radical type initiators if they are deposited on the substrate in the form of a solution / suspension which contains silicone epoxy monomers (ii).

The monomers of type (iii) are deposited on the substrate (for example by spraying) starting from a solution containing the same in mixture with the silicone compounds (ii), which form a protective layer above the surface of the monomer layer (iii). This protective layer is able to prevent oxygen from reaching the acrylic monomers. In this way it is not necessary to add radical polymerization initiators / catalysts.

Examples of monomers of type (iii) are acrylic acid and esters of acrylic and methacrylic acid, possibly perhalogenated, preferably perfluorinated, vinyl esters, possibly perhalogenated, preferably perfluorinated, vinyl ethers, possibly perhalogenated, preferably perfluorinated, vinyl halides, etc.

In particular, the perfluoroalkylesters of acrylic and methacrylic acid, and the perfluorovinylesters and ethers are used to impart oleophobicity.

Therefore the coatings obtained with the composition (B) impart water repellence to the substrate and in some cases can also impart oil repellence.

The method of the invention can also be used for the deposition of multifunctional coatings, in which nano and micro particles are incorporated in the plasma polymerized deposit. The nanoparticles and microparticles can be of metallic or non-metallic oxides or be made of metals or non-metals, such as Si and C, or organic particles, preferably in the form of nanometric powders with an average particle diameter preferably between 10 nm and 1 micron or in the form of micrometric particles with a diameter from 1 micron to tens of microns. The particles can be in full, porous or capsule form. Examples of oxides are for example silica, titanium dioxide, Zirconia, alumina, magnese oxide, nickel oxide, clays and zeolites. Examples of organic particles are: polypropylene, polyethylene or polystyrene microparticles or a mixture thereof.

In this case the composition (A) or (B) used in the method of the invention comprises nanoparticles which are in turn capable of conferring specific functionalities to the coating.

The compositions (A) and (B) used in the coating method according to the present invention can optionally contain one or more of the following additives usually used in conventional monomer compositions such as: pigments, inorganic fillers, organic dyes and inorganic UV stabilizers , antioxidants etc. The monomers of type (ii) commercial and above named with the trademark TEGO <®> may possibly contain photosensitizers based on isopropylthioxanthone.

The method object of the present invention can in particular be used on many types of materials such as for example: wood, paper, glass, metals, textile materials both in the form of fabric and non-woven fabric of an artificial type, for example polyesters and polyamides, of natural type, for example cotton, hemp, linen, or mixed type: artificial and natural, plastic, ceramic materials, composite materials such as polymeric materials reinforced with carbon fibers, with glass fibers and with ceramic material, building materials , furniture, multilayer materials.

The following examples of the method according to the present invention are reported for illustrative but not limitative purposes.

1-INTRODUCTION

The specifications of the materials of the substrates coated with the method object of the present invention are reported below.

MATERIAL DEFINITION

COTTON 1 (examples N ° 1, 6, 8): 100% cotton, weight 70 g / m <2>

COTTON 2 (examples N ° 9, 10, 15, 16): 100% cotton, weight 125 g / m <2>

PE (examples N ° 7, 14): LDPE (low density polyethylene), thickness 100 micron

PET fabric (example N ° 2): polyethylene terephthalate fabric with monofilament weaving. 31 micron wire diameter, 25 micron mesh opening.

PET fabric 2 (examples N ° 3, 17): polyethylene terephthalate fabric with monofilament weaving. 64 micron wire diameter, 35 micron mesh opening.

Nylon monofilament fabric (example N ° 12): nylon fabric with monofilament weaving. Wire diameter of 66 microns, mesh opening of 35 microns.

Paper (example N ° 5): lignocellulosic material weight 120 g / m <2>

Glass (example N ° 4): thickness 1 mm

Fabric 80% Nylon - 20% Elastane <®> (examples N ° 11, 13).

2. First part: the effects of the method of the invention conducted both in nitrogen and in air (open chamber) are studied and compared with the results obtained with a similar process carried out in the presence of catalysts.

2-1 COMPOSITION (A) with only the epoxy silicone monomer (ii)

EXAMPLE 1 - Treatments on cotton (COTTON 1)

Two cotton fabrics (COTTON 1) of 90 cm <2> each, are pre-activated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. A sample is sprayed with 3 ml of a 30 g / l solution of silicone epoxy (TEGO RC1409) in isopropanol using an airbrush. The second sample is sprayed with a 30 g / l solution of epoxy silicone (TEGO RC1409) in isopropanol containing a photoinitiator (TEGO PC 1466) in a concentration of 3% by weight of the epoxy monomer. The samples are finally treated in air plasma at atmospheric pressure with a planar reactor of the DBD type (4 passes at the speed of 7 m / min, linear power density of 20 W / cm). After the plasma treatment, the fabrics are heated in the oven at 120 ° C for 2 minutes.

The same is also repeated with nitrogen plasma (used in both pre-activation and treatment).

The characterization of the tissues is carried out by measuring the contact angle and the absorption time of water droplets with a volume of 50 microliters. Note that untreated cotton 1 absorbs the drop of water in 2 seconds and has an assumed contact angle value of 0 degrees.

Time Time Time Type of treatment absorption absorption 1 absorption 4

(min) day (min) days (min) Air with photoinitiator 38 ± 4 33 ± 6> 120 (evaporates) Air without photoinitiator 80 ± 10> 120 (evaporates)> 120 (evaporates) Nitrogen with photoinitiator> 120 (evaporates)> 120 (evaporates)> 120 (evaporates) Nitrogen without

22 ± 3 29 ± 2> 120 (evaporates) photoinitiator

Treatment type Contact angle (°) Air with photoinitiator 145 ± 9 Air without photoinitiator 150 ± 8 Nitrogen with photoinitiator 148 ± 4 Nitrogen without photoinitiator 146 ± 3

EXAMPLE 2 - Treatments on PET1

Two PET fabrics of 90 cm <2> each are pre-activated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. A sample is sprayed with 3 ml of a 30 g / l solution of silicone epoxy (TEGO RC1409) in isopropanol using an airbrush. The second sample is sprayed with a 30 g / l solution of epoxy silicone (TEGO RC1409) in isopropanol containing a photoinitiator (TEGO PC 1466) in a concentration of 3% by weight of the epoxy monomer. The samples are finally treated in air plasma at atmospheric pressure with a planar reactor of the DBD type (4 passes at the speed of 7 m / min, linear power density of 20 W / cm).

The characterization of the tissues is carried out by measuring the contact angle.

Angle of

Treatment type

contact (°)

PET n.t. 120 ± 3

With photoinitiator 136 ± 2

Without photoinitiator 135 ± 1

EXAMPLE 3 - Treatments on PET 2

Two different PET fabrics (PET 2) of 90 cm <2> each, are pre-activated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. A sample is sprayed with 3 ml of a 30 g / l solution of silicone epoxy (TEGO RC1409) in isopropanol using an airbrush. The second sample is sprayed with a 30 g / l solution of epoxy silicone (TEGO RC1409) in isopropanol containing a photoinitiator (TEGO PC 1466) in a concentration of 3% by weight of the epoxy monomer. The samples are finally treated in air plasma at atmospheric pressure with a planar reactor of the DBD type (4 passes at the speed of 7 m / min, linear power density of 20 W / cm). After the plasma treatment, the fabrics are heated in the oven at 120 ° C for 2 minutes.

The same is also repeated with nitrogen plasma (used in both pre-activation and treatment).

The characterization of the tissues is carried out by measuring the contact angle.

Type of treatment Contact angle (°) PET 2 untreated 95 ± 1

Air with photoinitiator 130 ± 4

Air without photoinitiator 134 ± 2

Nitrogen with photoinitiator 126 ± 1

Nitrogen without photoinitiator 128 ± 3

EXAMPLE 4 - Treatments on glass

Two glass plates are pre-activated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. A sample is sprayed with a 5 g / l solution of epoxy silicone (TEGO RC1409) in isopropanol. The second sample is sprayed with a 5 g / l solution of epoxy silicone (TEGO RC1409) in isopropanol containing a photoinitiator (TEGO PC 1466) in a concentration of 3% by weight of the epoxy monomer. The samples are finally treated in air plasma at atmospheric pressure with a DBD type planar reactor (2 passes at a speed of 7 m / min, linear power density of 20 W / cm).

The characterization is carried out by measuring the contact angle.

For comparison, a sample of glass only sprayed with a 5 g / l solution of silicone epoxy (TEGO RC 1409) in isopropanol is also prepared.

Angle of

Sample

contact (°)

Untreated glass 24 ± 2

Air treated with

105 ± 2

photoinitiator

Air treated without

101 ± 1

photoinitiator

Just sprayed

without 30 ± 3

photoinitiator

EXAMPLE 5 - Treatments on paper

Two paper samples are pre-activated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. A sample is sprayed with 3 ml of a 30 g / l solution of silicone epoxy (TEGO RC1409) in isopropanol using an airbrush. The second sample is sprayed with a 30 g / l solution of epoxy silicone (TEGO RC1409) in isopropanol containing a photoinitiator (TEGO PC 1466) in a concentration of 3% by weight of the epoxy monomer. The samples are finally treated in air plasma at atmospheric pressure with a planar reactor of the DBD type (4 passes at the speed of 7 m / min, linear power density of 20 W / cm).

The characterization is carried out by measuring the contact angle and the absorption time of water droplets with a volume of 50 microliters.

Time Angle of

Contact absorption sample (°)

(min)

Untreated card Instant 0

Card treated with

13 119 ± 6

photoinitiator

Card treated without

82 126 ± 1

photoinitiator

Examples 1-4 using composition (A) wherein the monomer is a type (ii) silicone epoxy show that:

· The method of the invention, which is carried out in the absence of an ionic photocatalyst, works like or even better than a similar process carried out in the presence of a photocatalyst.

· This occurs both in the presence of nitrogen only and in the air, in an open chamber.

2-1 COMPOSITION (A) with only the epoxy monomer (s)

EXAMPLE 6 - Treatments on cotton with epoxy decane (COTTON 1)

Two cotton fabrics (COTTON 1) of 90 cm <2> each, are pre-activated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. A sample is sprayed with 3 ml of a 10 g / l solution of epoxydecane in isopropanol using an airbrush. The second sample is sprayed with 10 g / l of epoxydecane in isopropanol containing a photoinitiator (TEGO PC 1466) in a concentration of 3% by weight of the epoxy monomer. The samples are finally treated in air plasma at atmospheric pressure with a planar reactor of the DBD type (4 passes at the speed of 7 m / min, linear power density of 20 W / cm). After the plasma treatment, the fabrics are heated in an oven at 120 ° C for 1 minute.

The same is also repeated with nitrogen plasma (used in both pre-activation and treatment).

The characterization of the tissues is carried out by measuring the contact angle and the absorption time of water droplets with a volume of 50 microliters.

For comparison, a single sample is also prepared sprayed with 3 ml of a 10 g / l solution of epoxydecane in isopropanol and heated in an oven at 120 ° C for 1 minute.

Time

Absorption treatment type

(min)

Air with photoinitiator 4

Air without photoinitiator 7

Nitrogen with photoinitiator 3

Nitrogen without

14

photoinitiator

Only sprayed and heated 2

This example shows that the method according to the present invention, which is carried out in the absence of an ionic photocatalyst, works as or even better than a similar process carried out in the presence of an ionic photocatalyst. This happens whether you operate in the presence of nitrogen only or in the presence of air, even in an open chamber.

EXAMPLE 7 - Treatments on PE with glycerol diglycidyl ether

Two PE films are pre-activated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. A sample is sprayed with a 10 g / l solution of glycerol diglycidyl ether in isopropanol. The second sample is sprayed with a 10 g / l solution of glycerol diglycidyl ether in isopropanol containing a photoinitiator (TEGO PC 1466) in a concentration of 3% by weight of the epoxy monomer. The samples are finally treated in air plasma at atmospheric pressure with a planar reactor of the DBD type (4 passes at the speed of 7 m / min, linear power density of 20 W / cm).

The same is also repeated with nitrogen plasma (used in both pre-activation and treatment).

The characterization is carried out by measuring the contact angle.

For comparison, only pre-activated films are prepared, only sprayed with a 10 g / l solution of glycerol diglycidyl ether in isopropanol (with and without photoinitiator), pre-activated and sprayed with a 10 g / l solution of glycerol diglycidyl ether in isopropanol (with and without photoinitiator).

Angle of

Sample

contact (°)

Untreated PE 90 ± 1

Air with

25 ± 2

photoinitiator

Air without

20 ± 2

photoinitiator

Nitrogen without

17 ± 1

photoinitiator

Just sprayed

without 86 ± 2

photoinitiator

Just sprayed with

72 ± 5

photoinitiator

Only pre-activated 41 ± 5

Pre-activated e

sprayed without 29 ± 1

photoinitiator

This example shows that the method according to the present invention, which is carried out in the absence of an ionic photocatalyst, works as or even better than a similar process carried out in the presence of an ionic photocatalyst. This happens whether you operate in the presence of nitrogen only or in the presence of air, even in an open chamber.

3. Second part modification of the surface properties with the method of the invention conducted in air (open chamber) with the composition (A), with the composition (B), with the composition (A) containing particles of titanium dioxide.

3.1 Modification of the surface properties with the method of the invention conducted in air (open chamber) with the composition (A) containing the monomer (ii)

EXAMPLE 8: preparation of water-repellent cotton fabrics (COTTON 1) A 90 cm <2> cotton fabric (COTTON 1) is pretreated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. 3 ml of a 30 g / l solution of epoxy silicone (TEGO RC1403) in isopropanol are sprayed onto the pretreated sample using an airbrush. The sample is then treated again in air plasma at atmospheric pressure with a DBD type planar reactor (4 passes at a speed of 7 m / min, linear power density of 20 W / cm). For comparison, a sample of cotton only sprayed with 3 ml of epoxy silicone isopropanol solution and a pretreated cotton sample (4 passes at a speed of 7 m / min, linear power density of 20 W / cm) and sprayed are also prepared with 3 ml of epoxy silicone isopropanol solution. The characterization of the tissues is carried out by measuring the absorption time of water droplets with a volume of 50 microliters and measuring the contact angle. The results are shown in the table.

TIME SAMPLE ANGLE ABSORPTION (s) CONTACT (°) COTTON 1 NON 0 (absorption

2

TREATED immediate) COTTON 1 ONLY 0 (absorption

2

SPRAYED immediate COTTON 1 2 0 (absorption PRE-TREATED AND immediate SPRAYED COTTON 1

PRE-TREATED - The drops evaporate without

143 ± 4 SPRAYED- absorb

TREATY

EXAMPLE 9: preparation of water-repellent cotton fabrics (COTTON 2) Three cotton fabrics different from the previous one (COTTON 2) of 90 cm <2> each, are pretreated in air plasma at atmospheric pressure with a planar reactor of the DBD type. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. The samples are then sprayed with 3 ml of a 30 g / l solution of silicone epoxy (TEGO RC1403) in isopropanol using an airbrush. The samples are finally treated in air plasma at atmospheric pressure with a planar reactor of the DBD type (4 passes at the speed of 7 m / min, linear power density of 20 W / cm). After the plasma treatment, the fabrics are heated in the oven at 120 ° C for different times (30 seconds, 1 minute, 2 minutes). For comparison, 3 samples of COTTON 2 are also prepared sprayed with 3 ml of a 30 g / l solution of epoxy silicone (TEGO RC1403) and heated in an oven without plasma treatment.

The characterization of the tissues is carried out by measuring the absorption time of water droplets with a volume of 50 microliters. The results are shown in Fig. 1, from which it can be seen how the plasma treatment leads to an increase in the water-repellent characteristics of the modified fabrics, much higher (5-7 times) than those coated with the same type of composition but not treated with plasma.

EXAMPLE 10: preparation of water-repellent cotton fabrics (COTTON 2) A cotton fabric (COTTON 2) of 90 cm <2> is pretreated in air plasma at atmospheric pressure with a planar reactor of the DBD type. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. 3 ml of a 10 g / l solution of 1,2-epoxy dodecane in isopropanol are sprayed onto the pretreated sample using an airbrush. The sample is then treated again in air plasma at atmospheric pressure with a DBD type planar reactor (4 passes at the speed of 7 m / min, linear power density of 20 W / cm) and heated in an oven for 5 minutes at 80 ° C. For comparison, a sample of cotton only sprayed with 3 ml of isopropanol solution of 1,2-epoxy dodecane and a pretreated cotton sample (4 passes at a speed of 7 m / min, linear power density of 20 W / cm) and sprayed with 3 ml of 1,2-epoxy dodecane isopropanol solution. The characterization of the tissues is carried out by measuring the absorption time of water droplets with a volume of 50 microliters and measuring the contact angle. The results are shown in the table.

TIME

CONTACT ANGLE ABSORPTION SAMPLE

(°)

(s)

COTTON 2 NOT

2 0 (immediate absorption) TREATED COTTON 2 ONLY

2 0 (immediate absorption SPRAYED COTTON 2 PRE-TREATED

2 0 (immediate absorption AND SPRAYED COTTON 2 The drops evaporate 126 ± 3

PRE-TREATED - without absorbing

SPRAYED-TREATED-OVEN

EXAMPLE 11 - Fabric treatments 80% nylon â € “20% elastane

A 90 cm <2> nylon (80%) and elastane (20%) fabric is pre-activated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. The sample is sprayed with 3 ml of a 30 g / l solution of epoxy silicone (TEGO RC1409) in isopropanol by means of an airbrush and then treated in air plasma at atmospheric pressure with a planar reactor of the DBD type (4 passes at the speed of 7 m / min, linear power density of 20 W / cm). After the plasma treatment, the fabric is heated in an oven at 120 ° C for 1 minute. The characterization of the tissues is carried out by measuring the absorption time of water droplets with a volume of 50 microliters and the contact angle.

Time Angle of

Contact absorption sample (°)

(min)

Non 0 fabric

Instant

treaty

Treated fabric 20 138 ± 3

EXAMPLE 12 - Nylon monofilament fabric treatments

A 90 cm <2> monofilament nylon fabric is pre-activated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. The sample is sprayed with 3 ml of a 30 g / l solution of epoxy silicone (TEGO RC1409) in isopropanol by means of an airbrush and then treated in air plasma at atmospheric pressure with a planar reactor of the DBD type (4 passes at the speed of 7 m / min, linear power density of 20 W / cm). After the plasma treatment, the fabric is heated in an oven at 120 ° C for 1 minute.

The characterization of the fabric is carried out by measuring the contact angle.

Angle of

Sample

contact (°)

Non fabric

112 ± 1

treaty

Treated fabric 129 ± 1

3.2 Modification of the surface properties with the method of the invention conducted in air (open chamber) with the composition (A) containing the monomer (i)

EXAMPLE 13 - Fabric treatments 80% nylon - 20% Elastane <®> with epoxy decane

A 90 cm <2> nylon (80%) Elastane <®> (20%) fabric is pre-activated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. The sample is sprayed with 3 ml of a 10 g / l solution of epoxydecane in isopropanol by means of an airbrush and then treated in air plasma at atmospheric pressure with a planar reactor of the DBD type (4 passes at a speed of 7 m / min, linear power density of 20 W / cm). After the plasma treatment, the fabric is heated in an oven at 120 ° C for 1 minute.

The characterization of the fabric is carried out by measuring the absorption time of water droplets with a volume of 50 microliters.

Time

Absorption sample

(min)

Non fabric

Instant

treaty

Treated fabric 4

EXAMPLE 14: Preparation of hydrophilic polyethylene (PE) films

A 90 cm <2> LDPE film is pretreated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pretreatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. 1 ml of a solution containing glycerol-diglycidyl ether (10 g / l) is sprayed onto the pretreated sample using an airbrush. The sample is then treated again in air plasma at atmospheric pressure with a DBD type planar reactor (4 passes at a speed of 7 m / min, linear power density of 20 W / cm). The characterization of the films is carried out by measuring the contact angle. The results are shown in the table.

CONTACT CORNER

SAMPLE

(°)

PE NOT TREATED 102 ± 5

PRE-TREATED PE-

20 ± 2

SPRAYED-TREATED

EXAMPLE 15: preparation of water-repellent and oil-repellent cotton fabrics A cotton fabric 2 of 90 cm <2> is pretreated in air plasma at atmospheric pressure with a planar reactor of the DBD type. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. 3 ml of a solution containing silicone epoxy (5 g / l) and perfluoro decyl acrylate (20 g / l) in isopropanol are sprayed onto the pretreated sample using an airbrush. The sample is then treated again in air plasma at atmospheric pressure with a DBD type planar reactor (4 passes at a speed of 7 m / min, linear power density of 20 W / cm). For comparison, a cotton fabric only sprayed with 3 ml of isopropanol solution of epoxy silicone (5 g / l) and perfluoro decyl acrylate (20 g / l) and a pretreated cotton fabric (6 passes at the speed of 2 , 5 m / min, linear power density of 13 W / cm) and sprayed with 3 ml of silicone epoxy isopropanol solution (5 g / l) and perfluoro decyl acrylate (20 g / l). The characterization of the fabrics is carried out by measuring the absorption time of water drops with a volume of 50 microliters, measuring the contact angle and evaluating the oil-repellent characteristics by means of a non-polar test kit (ISO 14 419). The results are shown in the table.

TIME ANGLE OF

KIT-TEST SAMPLE ABSORPTION CONTACT APOLAR WATER TO WATER (s) (°)

COTTON 2 NOT 0 (absorption

2 0 immediate TREATY)

COTTON 2

ONLY 0

SPRAYED COTTON 2

PRE-TREATED 0 AND SPRAYED COTTON 2

The drops

PRE-TREATED

evaporate without 135 ± 4 5-SPRAYED-absorb

TREATY

3.3 Modification of the surface properties with the method of the invention conducted in the air (open chamber) with the composition (B)

EXAMPLE 15: preparation of water-repellent and oil-repellent cotton fabrics A cotton fabric 2 of 90 cm <2> is pretreated in air plasma at atmospheric pressure with a planar reactor of the DBD type. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. 3 ml of a solution containing silicone epoxy (5 g / l) and perfluoro decyl acrylate (20 g / l) in isopropanol are sprayed onto the pretreated sample using an airbrush. The sample is then treated again in air plasma at atmospheric pressure with a DBD type planar reactor (4 passes at a speed of 7 m / min, linear power density of 20 W / cm). For comparison, a cotton fabric only sprayed with 3 ml of isopropanol solution of epoxy silicone (5 g / l) and perfluoro decyl acrylate (20 g / l) and a pretreated cotton fabric (6 passes at the speed of 2 , 5 m / min, linear power density of 13 W / cm) and sprayed with 3 ml of silicone epoxy isopropanol solution (5 g / l) and perfluoro decyl acrylate (20 g / l). The characterization of the fabrics is carried out by measuring the absorption time of water drops with a volume of 50 microliters, measuring the contact angle and evaluating the oil-repellent characteristics by means of a non-polar test kit (ISO 14 419). The results are shown in the table.

TIME ANGLE OF

ABSORPTION SAMPLE TEST KIT APOLAR CONTACT OR WATER (s) WATER (°)

COTTON 2 NOT 0 (absorption

2 0 immediate TREATY)

COTTON 2 ONLY

0 SPRAYED COTTON 2

PRE-TREATED 0

AND SPRAYED COTTON 2

The drops

PRE-TREATED-evaporate without 135 ± 4 5 SPRAY-absorb

TREATY

With this example it is shown that with the invention process it is possible to impart both hydro and oil repellency.

3.4 Modification of the surface properties with the method of the invention conducted in the air (open chamber) with the composition (A) containing nano particles.

EXAMPLE 16: deposition of coating incorporating nanoparticles on cotton (COTTON2)

A 90 cm <2> cotton (COTTON 2) fabric is pretreated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. 3 ml of a 30 g / l solution of epoxy silicone (TEGO RC1403) and 2.5 g / l of TiO2 nano particles (nominal mean diameter 25 nm) in isopropanol are sonicated for 5 minutes and sprayed on the pretreated sample using an airbrush . The sample is then treated again in air plasma at atmospheric pressure with a DBD type planar reactor (4 passes at a speed of 7 m / min, linear power density of 20 W / cm). Tissue characterization is performed by scanning electron microscopy (SEM).

EXAMPLE 17: preparation of super-water repellent polyester (PET) fabrics A 90 cm <2> PET 2 fabric is pretreated in air plasma at atmospheric pressure with a DBD-type planar reactor. The pre-treatment is carried out with 4 passes at a speed of 7 m / min and a linear power density of 20 W / cm. 3 ml of a 30 g / l solution of epoxy silicone (TEGO RC1403) in isopropanol are sprayed onto the pretreated sample using an airbrush. The sample is then treated again in air plasma at atmospheric pressure with a DBD type planar reactor (4 passes at a speed of 7 m / min, linear power density of 20 W / cm). A pretreated PET sample is also prepared, sprayed with 3 ml of epoxy silicone isopropanol solution (30 g / l) and TiO2 nano particles (5 g / l) and plasma treated. The characterization of the tissues is carried out by measuring the contact angle. The results are shown in the table.

SAMPLE CONTACT ANGLE

(°)

UNTREATED PET 95 ± 1

PRE-TREATED PET-

134 ± 2

SPRAYED-TREATED

PET PRE-TREATED-SPRAYED WITH TiO2- 141 ± 2

TREATY

The incorporation of nano particles leads to a slight increase in the contact angle, due to the resulting nano roughness.

Claims (13)

CLAIMS 1. A method of coating a substrate comprising the following steps: a) deposition on said substrate of a polymerizable composition selected from the following compositions: Composition (A) containing as essential component: at least one epoxy monomer (i) and / or one silicone epoxy monomer (ii); · Composition (B) containing as an essential component at least one silicone epoxy monomer (ii) and at least one monomer containing at least one ethylene unsaturation (iii); b) polymerization of said composition by plasma treatment. Method according to claim 1, wherein step (b) is conducted in an air plasma. Method according to claim 1 or 2, wherein in step (a) the composition (A) or (B) is in liquid form. Method according to claim 3, wherein said composition (A) or (B) is in the form of a monomer composition as such, it is in the form of a solution in organic solvent, in a mixture of organic solvent and water, or in the presence of water possibly added with surfactants. Method according to any one of claims 3 or 4, wherein said composition (A) or (B) in step (a) is deposited by means of the spray technique. Method according to any one of claims 1-5, wherein step (b) is carried out with a source of the dielectric barrier discharge type (DBD) and the distance of the composition (A) or (B) from the electrodes is between 0 and 3 cm. 7. Method according to any one of claims 1-6, characterized in that step (b) is carried out at temperatures below 150 ° C, at frequencies ranging from 0.5kHz to 1MHz at a pressure ranging from 90% to 150% of the ambient pressure or even more preferably at 1 atm, at operating powers between 1W / cm and 300 W / cm, preferably between 1W / cm and 30W / cm. Method according to any one of claims 1-7, comprising prior to step (a) a plasma pretreatment of the substrate to be coated. Method according to any one of claims 1-8 wherein the epoxy monomer (i) contained in composition (A) is preferably selected from the class consisting of glycidol, glycol diglycidyl ether, 1,3-diglycidylglyceryl ether, glycidyl methacrylate, bisphenol A diglycidyl ether, 1,2 epoxydecane, glycerol diglycidyl ether, glycidyl octafluoropentyl ether, propylene oxide, glycidyl methyl ether, glycidyl butyrate, epoxyoctane, glycidyl tosylate, diepoxyoctane, furfuryl glycidyl ether, (2,2,3,3,4,4, 5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl) oxirane. Method according to any one of claims 1-9, wherein the silicone epoxy monomer of type (ii) contained in composition (A) or (B) is selected from low molecular weight and preferably low viscosity epoxy silicone monomer or a C1-C4-alkyl siloxane oligomer / polymer, being terminated and / or substituted in the chain with at least one C1-C6alkylene (C5-C6-cycloalkylene) -epoxide residue. 11. Method according to any one of claims 1-8 and 10, wherein the monomer (iii) contained in composition (B) is selected from the group consisting of esters of acrylic and methacrylic acid optionally for halogenated preferably perfluorinated, vinyl esters optionally perhalogenated, preferably perfluorinated, optionally perhalogenated vinyl ethers, preferably perfluorinated, vinyl halides, etc. Method according to any one of claims 1-11, wherein the composition (A) or (B) comprises nanoparticles of metals or non-metals or of metallic or non-metallic oxides, preferably TiO2. 13. Coated substrate obtained by plasma polymerization of a monomer composition selected from: composition (A) containing as an essential component: at least one epoxy monomer (i) and / or a silicone epoxy monomer (ii); composition (B) containing as an essential component at least one silicone epoxy monomer (ii) and at least one monomer containing at least one ethylene unsaturation (iii), characterized in that the coating obtained is free of ionic photocatalysts.